EP1556740B1 - Ionic photoacid generators with segmented hydrocarbon-fluorocarbon sulfonate anions - Google Patents

Ionic photoacid generators with segmented hydrocarbon-fluorocarbon sulfonate anions Download PDF

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Publication number
EP1556740B1
EP1556740B1 EP03777730A EP03777730A EP1556740B1 EP 1556740 B1 EP1556740 B1 EP 1556740B1 EP 03777730 A EP03777730 A EP 03777730A EP 03777730 A EP03777730 A EP 03777730A EP 1556740 B1 EP1556740 B1 EP 1556740B1
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Prior art keywords
group
photoacid generator
ionic
groups
acid
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German (de)
English (en)
French (fr)
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EP1556740A2 (en
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William M. Lamanna
Gregory D. Clark
Richard M. Flynn
Zai-Ming Qiu
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/115—Cationic or anionic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/122—Sulfur compound containing

Definitions

  • the invention relates to ionic photoacid generators (PAGs).
  • the invention further relates to photosensitive compositions containing these ionic photoacid generators, a method of preparing a photoresist pattern and a method of making a polymer.
  • Ionic photoacid generators comprising an organic onium or organometallic cation and a non-nucleophilic counter anion have been shown to have utility as photochemically activated initiators for cationic addition polymerization in negative resists and polymer coating formulations or as similarly activatable latent acid catalysts for step-growth (or condensation) polymerization, depolymerization and the deprotection of functionalized polymers used in positive, chemically amplified photoresists.
  • Common commercial ionic PAGs include onium and organometallic salts such as diaryliodonium and triarylsulfonium salts and (cyclopentadienyl)(arene)iron + salts of the anions PF 6 - , SbF 6 - , CF 3 SO 3 - , C 4 F 9 SO 3 - and C 8 F 17 SO 3 - .
  • these same salts may also photoinitiate free-radical addition polymerization and are useful in "dual cure” applications where a mixture of cationically sensitive and free-radically polymerizable monomers are polymerized either simultaneously or sequentially.
  • certain classes of these salts are known to be thermally-activatable curatives for cationic, step-growth and free-radical polymerizations.
  • PAGs are the photoactive ingredients in photoresists that produce acid upon irradiation.
  • this photoacid In a positive resist this photoacid generally serves to catalyze deprotection of the polymeric resist, thereby altering its solubility in a developer.
  • the photoacid In a negative resist the photoacid typically initiates cationic polymerization or curing of monomeric groups, resulting in crosslinking of the resin in the irradiated areas.
  • Organic onium salts are particularly useful as PAGs in chemically amplified photoresist applications owing to their high quantum efficiency for acid production at commonly used exposure wavelengths.
  • positive photoresists used in semiconductor microlithography a number of other features and functional properties have been identified as being critical to PAG performance. These include: 1) compositions that are free of metallic or semimetallic elements (i.e., dopant elements) that can alter the electronic properties of the semiconducting substrate (e.g., silicon), 2) high photoacid strength, 3) low photoacid volatility, 4) small photoacid diffusion length, 5) solubility, and 6) thermal stability.
  • PAG anions that provide both the requisite balance of properties as well as an acceptable EHS+R (environmental, health, safety and regulatory) profile for use in semiconductor photoresists. Consequently, the selection of ionic PAGs for semiconductor photoresist applications has become anion limited and there exists a pressing need within the industry for a greater selection of semiconductor-compatible PAG anions that offer desirable photoresist performance, along with safety and environmental sustainability.
  • Ionic PAGs have additional utility in the preparation of polymer coatings, sealants, encapsulants, and the like derived from cationically polymerizable monomers and oligomers.
  • the polymerizable monomers are multifunctional (i.e., contain more than one polymerizable group per molecule), for example, epoxides, such as diglycidyl ethers of bisphenol A (DGEBA) and vinyl ethers, such as 1,4-cyclohexanedimethanol divinyl ether (CHVE).
  • DGEBA diglycidyl ethers of bisphenol A
  • CHVE 1,4-cyclohexanedimethanol divinyl ether
  • Multifunctional monomers such as polyisocyanates and polyalcohols (polyols) or polyepoxides and polyalcohols can undergo acid-catalyzed polycondensation via a step-growth mechanism.
  • multireactive monomers those that comprise two or more classes of reactive groups, such as, for instance, a monomer comprising both acrylate and isocyanate functionalites.
  • ionic PAGs particularly those based on iodonium, sulfonium, diazonium, phosphonium and organometallic complex cations.
  • the nature of the counteranion in a complex salt can influence the rate and extent of cationic addition polymerization.
  • J.V. Crivello, and R. Narayan, Chem. Mater ., 4, 692, (1992) report that the order of reactivity among commonly used nonnucleophilic anions is SbF 6 - > AsF 6 - > PF 6 - > BF 4 - .
  • the influence of the anion on reactivity has been ascribed to three principle factors: (1) the acidity of the protonic or Lewis acid generated, (2) the degree of ion-pair separation in the propagating cationic chain and (3) the susceptibility of the anions to fluoride abstraction and consequent chain termination.
  • DD 295421 (Wilpert ) describes positive photoresist with chemical enhancement that contains a poly-tert.butoxy-carbonyl-oxy-styrene (I), a solvent (mixt.) (II) and, as photosensitive component, a triarylsulphonium salt in a concentration of 4-25 (wt.)% w.r.t. total solids.
  • the resist is sensitive to exposure at wavelengths in the 190-360 nm range and useful in the production of microelectronic components.
  • WO 02/082185 (Ferreira ) describes a photoacid compound that has a general structure R-O(CF 2 ) n SO 3 X.
  • the photoacid compound is useful for photoresist compositions as electroplating resist, plasma etch resist, solder resist, resist for producing printing plates, resist for chemical milling or resist for producing integrated circuits and used in electronic industry.
  • U.S. Patents No. 4,920,182 and 4,957,946 describe energy-polymerizable compositions comprising arene-iron salts of, e.g ., fluoroalkylsulfonic acid (fluoroalkylsulfonates).
  • U.S. Patent No. 5,089,536 describes energy-polymerizable compositions comprising organometallic salts as initiators. Numerous anions are disclosed as being suitable counterions for the organometallic cations disclosed therein.
  • Patents DD 295,421 and US Pat No. 6,358,665 disclose ionic photoacid generators comprising I- and S-centered onium cations and organic sulfonate anions with various degrees of fluorination of the organic group.
  • Photoactive cationic nuclei, photoactive cationic moieties, and photoactive cationic organic compounds are art recognized classes of materials as exemplified by U.S. Patent Nos. 4,250,311 ; 3,708,296 ; 4,069,055 ; 4,216,288 ; 5,084,586 ; 5,124,417 ; 4,985,340 and 5,089,536 .
  • ionic photoacid generators having (1) a photoactive cation comprising at least one of (i) a transition metal containing organometallic cation, (ii) an organic onium cation, such as an iodonium or sulfonium cation, or (iii) a mixture thereof, and (2) a segmented hydrocarbon-fluorocarbon-sulfonate anion of the formula (I): - O 3 S-R f -Q-(R h -Z m ) n (I) where:
  • this invention relates to chemically amplified photoresist compositions that may be imaged by selective exposure to actinic radiation.
  • the photoresist compositions comprise at least one ionic photoacid generator of the present invention, dispersed or dissolved in a suitable resist polymer matrix.
  • the photoresist compositions are typically utilized in the form of a thin film coating on an appropriate substrate, such as a silicon wafer and are useful, for example, in the patterning of silicon chips used in the manufacture of integrated circuits.
  • Chemically amplified resist systems based upon acid catalyzed chain reactions are recognized in the art as a preferred class of resist systems for micro- or nanolithography due to the high spectral sensitivity provided by the acid-catalyzed or initiated chemical amplification mechanism, and the insensitivity of such systems to oxygen, a common inhibitor of free radical processes.
  • Ionic photoacid generators comprising photoactive cationic moieties and segmented, highly fluorinated-hydrocarbon anionic moieties exhibit improved solubility in organic media, and provide acids with high acid strength and/or very strong catalytic activity. These anions are stable, and non-nucleophilic, yet they do not contain highly toxic elements such as arsenic and antimony or semiconductor incompatible elements such as B and P.
  • the initiating, curing, and/or catalytic activity of certain ionic photoacid generators and their solubility in organic compounds can be improved by using particular classes of counter-anions in association with cationic groups thereof to form thermal- or photoactive catalyst generating materials.
  • the compounds of this invention shall be referred to as photoacid generators that can be activated using many different forms of energy activation, including, but not limited to photoactivation, electron beam activation, and other electromagnetic radiation activation that stimulates, activates, or releases the active species.
  • the catalyst-generating materials of the present invention can display improved solubility in organic media, particularly low polarity media such as energy-curable monomers and non-polar organic polymers or solvents such as ketones (e.g., methyl ethyl ketone), ethers, esters, methylene chloride, and the like.
  • organic media particularly low polarity media such as energy-curable monomers and non-polar organic polymers or solvents such as ketones (e.g., methyl ethyl ketone), ethers, esters, methylene chloride, and the like.
  • Chemically amplified photoresists are advantageous in that the catalytic imaging process can provide high photosensitivity. By virtue of their high photosensitivity and high resolution, chemically amplified photoresists are being utilized in most state of the art or next generation microlithography systems.
  • Chemically amplified photoresists comprise a radiation sensitive, photoacid generator (PAG) that acts as a latent source of photogenerated acid. Upon exposure to actinic radiation, the photoacid generator releases an acid that subsequently catalyzes a chemical reaction in the surrounding medium in which the PAG is dissolved, generally an acid sensitive polymer.
  • PAG radiation sensitive, photoacid generator
  • solubility of the photoresist increases during exposure to radiation it is termed a positive resist; if the solubility decreases it is termed a negative resist.
  • Today's most common positive resists generally function by acid catalyzed cleavage of acid-sensitive protecting (or blocking) groups attached to a polymer chain, which, once removed, render the polymer soluble in developer.
  • Negative resists generally involve an acid catalyzed or initiated crosslinking reaction that renders the composition insoluble, usually via polymerization of pendant monomeric groups.
  • positive-working chemically amplified photoresists generally contain two-components comprising (i) a polymeric resin which has been rendered insoluble in alkaline solutions by masking at least a part of the water soluble groups on the resin with an acid cleavable protecting group and (ii) a photoacid generator.
  • Other materials can be optionally added to improve lithographic performance such as bases and dissolution inhibitors.
  • the photoacid generator Upon exposure to actinic radiation, the photoacid generator produces a strong acid capable of catalytically cleaving the bond between the protecting groups and the resin, resulting in the formation of an alkali-soluble resin.
  • a single photogenerated acid molecule is able to cleave a large number of protecting groups from the resin, thus contributing to the high sensitivity of chemically amplified positive photoresists.
  • Negative working photoresists generally contain a cross-linking agent or a polymerizable group linked to a soluble polymer or oligomer.
  • the acid produced from exposure of the photoacid generator causes the exposed area to become crosslinked and therefore insoluble in developer.
  • the invention further comprises a photoresist coating composition comprising:
  • the invention further provides a method of preparing a photoresist pattern comprising the steps of coating a substrate with a mixture of a resist polymer and the photoacid generator of the present invention, and selectively irradiating said coating to activate said photoacid generator.
  • the method may further comprise the step of heating said irradiated coating at elevated temperatures to effect differential solubility of said irradiated regions and the step of developing said irradiated coating to selectively dissolve soluble portions of the irradiated coating.
  • the invention additionally provides polymerizable compositions comprising (1) at least one of cationic addition polymerizable monomers, ethylenically-unsaturated free-radically polymerizable monomers, polymerizable by acid-catalyzed step-growth and combinations thereof; and (2) the photoacid generator of the present invention.
  • the ionic photoacid generators of the present invention comprising photoactive cationic moieties and segmented hydrocarbon-fluorocarbon-sulfonate anion moieties, produce photogenerated acids that are the conjugate acids of the PAG anions and, by virtue of their segmented structure, having a highly fluorinated organic group immediately adjacent to the sulfonic acid moiety, provide high acid strength and very strong catalytic activity.
  • This feature results in fast photospeeds when the photoacid generators are employed in positive resist formulations and rapid cure speeds when used in polymerizable compositions and in negative resists.
  • the segmented PAG anions are stable to elevated temperatures commonly used in resist processing, and they do not contain highly toxic elements such as arsenic and antimony or semiconductor incompatible (i.e., dopant) elements such as phosphorous and boron.
  • Yet another advantage is the ease of tailoring the overall size, shape and polarity, of the segmented anions and therefore the diffusivity, solubility and volatility, of the photoacid, while minimizing the chain length of the highly fluorinated R f segment.
  • large or high molecular weight PAG anions are preferred in today's advanced positive photoresist compositions because their conjugate acids are slow to diffuse in the resist polymer matrix and have low volatility, properties which are important to achieving high resolution and good image quality, respectively.
  • certain large perfluorinated PAG anions such as C 8 F 17 SO 3 - (PFOS)
  • PFOS perfluorinated PAG anions
  • segmented PAG anions of the present invention contain reactive functionalities such as C-H bonds, ether linkages, amide or ester groups, and the like that may be susceptible to chemical attack or physical degradation.
  • segmented fluoroorganic anions are expected to more readily degrade in the environment by, for example, some combination of photochemical, hydrolytic, chemical or biological attack on the hydrocarbon group, R h , or the linking group, Q, to produce relatively small fluorinated fragments that are nonbioaccumulative.
  • they are expected to have relatively short environmental lifetimes and be relatively benign in terms of their potential impact on the environment and living organisms.
  • alkyl refers to straight or branched, cyclic or acyclic hydrocarbon radicals, such as methyl, ethyl, propyl, butyl, octyl, isopropyl, tert-butyl, sec-pentyl, and the like.
  • Alkyl groups include, for example, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 6 carbon atoms.
  • alkenyl refers to straight or branched unsaturated hydrocarbon radicals having one or more double bonds, such as ethylene, propylene, butylene, 1, 3-pentadiene, 1, 4-pentadiene, and the like.
  • Alkenyl groups include, for example, 2 to 12 carbon atoms, or 2 to 9 carbon atoms.
  • alkylene refers to a divalent straight or branched saturated hydrocarbon radical such as, for example, -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH(CH 3 )CH 2 -, -CH 2 CH(CH 2 CH 3 )CH 2 CH(CH 3 )CH 2 -, and the like.
  • Alkylene groups include, for example, 1 to 20, 1 to 12, or 1 to 4 carbon atoms.
  • oxaalkylene refers to an alkylene group as defined above where one or more non-adjacent -CH 2 - groups have been substituted with a catenary oxygen atom, such as -CH 2 CH 2 OCH(CH 3 )CH 2 -,
  • aryl refers to monovalent unsaturated aromatic carbocyclic radicals having a single ring, such as phenyl, or multiple condensed rings, such as naphthyl or anthryl.
  • alkoxy refers to -O-alkyl with alkyl as defined above.
  • Alkoxy groups include, for example, methoxy, ethoxy, propoxy, isopropoxy, and the like.
  • perfluororalkylene refers to a fully fluorinated divalent straight or branched, cyclic or acylclic, saturated hydrocarbon radical such as, for example, -CF 2 -,-CF 2 CF 2 -, -CF 2 CF 2 CF 2 -, -CF 2 CF 2 CF(CF 3 )CF 2 -, and the like.
  • Perfluoroalkylene groups included 2 to 7 carbon atoms.
  • perfluorooxyalkylene refers to a perfluoroalkylene group as defined above where one or more non-adjacent -CF 2 - groups have been substituted with a catenary oxygen atom such as, for example, -CF 2 CF 2 OCF(CF 3 )CF 2 -, and the like.
  • Perfluorooxyalkylene groups include 2 to 7 carbon atoms, and preferably comprise perfluoroalkylene units of 2 to 3 carbon atoms.
  • weight percent refers to the percent by mass of an individual component in a total system.
  • weight percent of an individual monomer in a polymer is the mass of the individual monomer divided by the mass of the total polymers multiplied by 100.
  • multifunctional means the presence of more than one of the same functional reactive group in a monomer; “multireactive” means the presence of two or more of two different functional reactive groups; “acid catalyst” or “acid catalyzed” means catalysis by a Brönsted- or Lewis-acid species; and “molecular weight” means number average molecular weight (M n ), unless otherwise specified.
  • the present invention provides ionic photoacid generators comprising a photochemically-reactive cationic portion and a segmented hydrocarbon-fluorocarbon-sulfonate anion.
  • Ionic photoacid generators in which the anion comprises a highly fluorinated alkylene moiety and a hydrocarbon moiety, defined as segmented, display improved solubility in organic systems and/or generate a highly reactive initiator, curative, or catalyst upon energy activation.
  • the salts of the present invention further avoid the use of salts of toxic elements such as arsenic and antimony, or semiconductor-incompatible elements such as B and P, and are relatively inexpensive to manufacture.
  • Anions useful as the anionic portion of the ionic PAG salts of the present invention may be generally represented by Formula (I), respectively, and hereinafter referred to as segmented anions.
  • ionic photoacid generators wherein the ionic photoacid generator has (1) a cation comprising at least one of (i) a transition metal containing organometallic cation, (ii) an organic onium cation, or (iii) a mixture thereof, and (2) an anion of the formula: - O 3 S-R f -Q-(R h -Z m ) n (I) where:
  • the R f perfluoroalkylene chains may be unbranched, branched, acyclic or cyclic, saturated or unsaturated, and preferably are acyclic and saturated. Heteroatoms or radicals such as divalent oxygen, trivalent nitrogen or hexavalent sulfur may interrupt the skeletal chain, as is well recognized in the art.
  • R f is or contains a cyclic structure, such structure preferably has 5 or 6 ring members, 1 or 2 of which can be heteroatoms.
  • the linking group Q can be a covalent bond.
  • suitable divalent Q linking groups include the following: -C(O)O-, -C(O)S-, -SO 2 O-, -SO 2 S-, -S-, -S(O)- and -SO 2 -.
  • R h is independently selected from cyclic or acyclic, branched or unbranched, saturated or unsaturated organic hydrocarbon radicals having from 1 to 20 carbon atoms. Preferably R h has 1-8 carbon atoms.
  • R h or R 1 may comprise polymerizable groups, such as olefinic moieties.
  • Z is a pendant group selected from the group consisting of -Cl, -Br, -I, -NO 2 , -SO 3 - , -H, -CN, -NCO, -OCN, -CO 2 - , -OH, -OR 1 ', -SR 1 ', -C(O)N(R 1 ') 2 , -N(R 1 ')C(O)R 1 ', -N(R 1 ')SO 2 R 1 ', -SO 2 N(R 1 ') 2 , -SO 2 R 1 ', SOR 1 ', -OC(O)R 1 ', -C(O)OR 1 ', -C(O)R 1 ', -Si(OR 1 ') 3 , -Si(R 1 ') 3 , and an epoxy group; where R 1 ' is independently H, an unbranched or branched, cyclic or acyclic
  • fluorine-containing ionic PAG compositions which are effective in providing desired photoresist performance, and which eliminate more effectively from the body (including the tendency of the composition and/or its degradation products).
  • the preferred ionic photoacid generators of the present invention which contain anions with relatively short fluoroalkylene segments ( ⁇ 8 fluorinated carbon atoms), and reactive hydrocarbon segments, when exposed to biological, thermal, oxidative, hydrolytic, and photolytic conditions found in the environment, will break down to functional, short chain fluorocarbon degradation products that will not bio-accumulate.
  • R f group in Formula I include perfluoralkylene groups, -C m F 2m -, and perfluorooxaalkylene groups,-(C m F 2m O) o -C n F 2n -, containing a total of no more than 7 carbon atoms, preferably no more than 4 carbon atoms.
  • Difunctional or cyclic fluorochemical intermediates that are useful in preparing segmented anions of the present invention using methods that are generally known in the art include:
  • Cations useful as the cationic portion of the catalysts and initiators of the invention include:
  • Organometallic salts are known in the art and can be prepared as described in, for example, EPO No. 094,914 and U.S. Patent Nos. 5,089,536 , 4,868,288 , and 5,073,476 .
  • the organometallic initiators of the present invention are generally stable and active under ambient conditions that may include normal levels of atmospheric oxygen and water.
  • Examples of preferred cations for use in PAG compositions of the present invention include, but are not limited to the onium cations: diphenyliodonium, ditolyliodonium, didodecylphenyliodonium, (4-octyloxyphenyl)phenyliodonium, and bis(methoxyphenyl)iodonium; triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, 1,4-phenylene-bis(diphenylsulfonium); bis-(4-t-butylphenyl)-iodonium, (4-t-butyl-phenyl)-diphenyl-sulfonium, tris-(t-butylphenyl)-sulfonium, (4-butoxy-phenyl)-diphenylsulfonium, 1-(2-naphthalen-2-yl-2-oxoethyl)-te
  • ionic PAGs of the instant invention can be prepared by ion exchange or metathesis reactions by combining onium or organometallic salts that contain conventional counteranions, such as chloride, bromide, acetate, triflate, PF 6 - , SbF 6 - or BF 4 - , with simple alkali or alkaline earth metal salts or ammonium salts of the segmented anions of the invention in a suitable solvent.
  • conventional counteranions such as chloride, bromide, acetate, triflate, PF 6 - , SbF 6 - or BF 4 -
  • metathesis reactions may be carried out at temperatures ranging from about -80 to about 100°C, preferably at ambient temperature, under conditions in which either the PAG salt of the instant invention or the metathesis byproduct(s) selectively precipitates, thus permitting isolation of the salt of the invention in the form of a solution or a pure solid.
  • ion exchange may be carried out in a mixed solvent system where one of the solvents is water and the other solvent is a non-miscible organic solvent and the ionic PAG products are separated from the byproducts of ion exchange by selective partitioning to the separate phases. Normally the ionic PAGs of the present invention partition into the organic phase and the byproduct salts partition into the aqueous phase.
  • Separation may be achieved using a separatory funnel or similar device. Further purification may be achieved by washing the organic solution of the ionic PAG product with pure water to remove residual salt contaminants. The ionic PAG may then be isolated by stripping the organic solvent or by precipitation or recrystallizaton with a nonsolvent.
  • Suitable metathesis solvents generally are capable of dissolving at least one and preferably all of the reagents required for the metathesis reaction without reacting with these reagents. Solvents are generally selected such that the desired salt or the metathesis byproducts selectively precipitate, thus allowing the desired salt to be isolated in relatively pure form. Where a mixture of water and an organic solvent is used, the organic solvent is typically chosen based on its ability to selectively extract the desired ionic PAG product, while leaving the starting materials and the byproduct salts in the aqueous solution. Normally, the preferred solvent for a particular system is determined empirically.
  • Nonlimiting examples of suitable solvents include, water; chlorocarbons, such as methylene chloride, and chloroform; ethers; aromatic hydrocarbons, such as toluene, and chlorobenzene; nitriles, such as, acetonitrile; alcohols, such as methanol and ethanol; nitrobenzene; nitromethane; ketones, such as acetone and methyl ethyl ketone; and other similar classes of organic solvents.
  • Mixtures of solvents are often desirable to control solubility of reagents and product salts.
  • cationic organometallic catalysts employing the counterions of the invention can be prepared in, e.g ., protic solvents and in the presence of oxygen, in contrast to certain known organometallic catalysts used.
  • the PAG salts of the invention will form in situ if the individual PAG precursors described supra are added directly to the polymerizable or resist composition and a suitable solvent or diluent, including monomer, is used. It is preferred, however, to form the pure catalyst or initiator in a separate step as a solid or in a suitable solvent prior to adding the same to the polymerizable or resist composition and performing the photochemical process.
  • PAG salts of the above described anions and cations may be activated by radiation or may require two stage activation involving radiation followed by heat.
  • Suitable salts having photoactivatable cations and a segmented anion for use in the polymerizable or resist compositions of the instant invention are those salts that upon application of sufficient energy; accelerated particle (electron beam, ion beam), or electromagnetic radiation sources employing x-ray, extreme-UV, deep-UV, mid-UV near-UV and visible radiation will generate an acid species capable of initiating or catalyzing the desired polymerization, depolymerization, or deblocking chemistry.
  • the level of photocatalyst or initiator activity, and the preferred wavelength of actinic radiation will of course depend on the choice of cation and segmented anion in the ionic PAG and on the monomer or resist system chosen.
  • the present invention provides novel chemically amplified photoresist compositions that may be imaged by selective exposure to actinic radiation.
  • the photoresist compositions comprise photochemically active salts of the segmented fluoroorganic anions, described above, dispersed or dissolved in a suitable resist polymer matrix.
  • a coating solvent may also be present.
  • the photoresist compositions are typically utilized in the form of a thin film coating on an appropriate substrate, such as a silicon wafer, various metal clad substrates used in manufacturing circuit boards or a metal printing plate.
  • the photoresist films are generally coated from a photoresist solution comprising the ionic PAG, the resist polymer and a coating solvent using solution-coating techniques, such as spin coating.
  • Coating solvents that may be used to prepare thin film photoresist compositions of the present invention include, but are not limited to, propyleneglycol methyl ether acetate (PGMEA), ethyl lactate, ethyl acetate, cyclohexanone, and super critical carbon dioxide.
  • PGMEA propyleneglycol methyl ether acetate
  • ethyl lactate ethyl lactate
  • ethyl acetate cyclohexanone
  • super critical carbon dioxide super critical carbon dioxide
  • Selective irradiation of the photoresist coating is typically achieved by exposure through a mask, although other selective irradiation techniques may also be employed, such as laser writing. Upon irradiation, the photoactive salts undergo photochemical decomposition to produce a mixture of highly reactive products, including strong acid and free radicals.
  • Suitable polymers useful as photoresist matrix materials contain functional groups that are reactive towards the photochemically produced acid or free-radicals.
  • the polymer functional groups undergo secondary, non-photochemical chain reactions with these highly reactive species, a chemical amplification process that ultimately alters the solubility or volatility of the polymer in the irradiated regions.
  • Photoresist compositions that increase in solubility (or volatility) upon exposure to actinic radiation are termed positive photoresists, whereas, those that decrease in solubility are termed negative photoresists.
  • Changes in solubility can result, for example, from radical-or acid-induced crosslinking of the polymer, as in a negative photoresist, or from acid-catalyzed cleavage of polymer functional groups and conversion of the polymer to a more soluble or volatile form, as in a positive photoresist.
  • These secondary reactions may occur under ambient conditions or in a post-bake step carried out at elevated temperatures.
  • the differential solubility produced in the irradiated and non-irradiated portions of the polymer is sufficient to allow selective dissolution of only the more soluble portions of the exposed photoresist layer using a developer solution, thus creating a relief image.
  • Developer solutions may be organic or aqueous based mixtures or solutions, but typically comprise a dilute solution of aqueous base.
  • acid-catalyzed cleavage of functional groups in the main backbone of a polymer chain may produce only low molecular weight, volatile products which are liberated from the irradiated regions under appropriate conditions, thus negating the need for post-exposure development with solvents.
  • ionic photoacid generators containing organic onium cations are preferred over the ionic photoacid generators containing organometallic complex cations because metal-containing organometallic complex cations may introduce unwanted metal contaminants into the semiconductor chip manufacturing process.
  • Chemically amplified resist systems based upon acid catalyzed chain reactions are recognized as a preferred class of resist system for micro- or nanolithography due to the high spectral sensitivity provided by the acid-catalyzed or initiated chemical amplification mechanism and the insensitivity of such systems to oxygen, a common inhibitor of free radical processes. It is also recognized that positive-working photoresists are generally capable of providing better image resolution than negative working photoresists and are therefore preferred in applications where very fine-line image resolution is required, as in the manufacture of semiconductor devices.
  • Polymers useful as matrix materials for photoresists of the present invention may be chosen from any of a wide variety of polymer structures possessing functional groups that are reactive with acid or free radicals.
  • the functional groups may be present as pendant groups attached to the polymer chain, terminal end-groups, or may be contained within the polymer backbone itself
  • Common free radical- or acid-polymerizable functional groups useful in preparing negative photoresists which crosslink upon exposure include but are not restricted to epoxy groups, alcohol groups, acrylate groups, acrylamide groups, vinyl ether groups, olefinic groups, vinyl amine groups, cyclic ether groups, cyclic ester groups, cyclic carbonate groups, cyclic acetal groups, oxazoline groups, alkoxysilane groups, cyclosiloxane groups and mixtures thereof.
  • Acid labile functional groups that are useful in the preparation of positive photoresists include but are not restricted to ester groups (especially t-butyl esters, t-adamantyl esters, secondary allylic esters, secondary beta-ketoesters, alpha-tetrahydropyran esters and alpha-tetrahydrofuran esters), carbonate groups (especially t-butyl carbonates), silyl ether groups, acetal and ketal groups, and ether groups (especially t-butyl ethers).
  • Positive photoresists may also be obtained by incorporating low molecular weight, acid labile dissolution inhibitors such as t-butylcholate into a resin matrix.
  • Polymer backbones useful in photoresist compositions of the present invention span a wide range of structural types and are usually chosen based upon the particular balance of optical, chemical and physical properties desired for a given application. Important considerations in choosing a suitable polymer backbone include optical clarity, transmittance at the irradiating frequency, refractive index, adhesion to the substrate, plasma etch resistance, solubility and film forming characteristics.
  • Polymer backbones commonly employed in photoresist applications and suitable for use in the present invention include, but are not restricted to, polyphthaldehyde, polyacrylates, polymethacrylates, polystyrenes, polycycloolefins (including polymers derived from radical, ROMP and transition metal-catalyzed addition polymerization of norbornene and related polycyclic olefins), polycycloolefin-maleic anhydride copolymers, copolymers of fluoroolefins with cycloolefins, and phenol-formaldehyde condensation polymers.
  • Various copolymers of the above named homopolymers can also be used.
  • Resist compositions of this invention may be applied, preferably as a liquid, to a substrate such as a silicon wafer, steel, aluminum, copper, cadmium, zinc, ceramic, glass, paper, wood or various plastic films such as poly(ethyleneterephthalate), plasticized poly(vinylchloride), polypropylene, polyethylene, polyimide, and the like, and irradiated and/or heated.
  • a substrate such as a silicon wafer, steel, aluminum, copper, cadmium, zinc, ceramic, glass, paper, wood or various plastic films such as poly(ethyleneterephthalate), plasticized poly(vinylchloride), polypropylene, polyethylene, polyimide, and the like
  • plastic films such as poly(ethyleneterephthalate), plasticized poly(vinylchloride), polypropylene, polyethylene, polyimide, and the like
  • ionic PAG containing resist compositions of this invention may be used in the production of articles useful in the graphic arts, recording, and electronics industries, such as integrated circuit
  • a variety of additives and adjuvants may be added to positive and negative resist compositions of the invention to improve resist performance, including sensitizers, dissolution inhibitors, surfactants, leveling agents, bases or acid scavengers and stabilizers.
  • Art-known PAGs either neutral or ionic, may also be used in combination with the ionic PAGs of the present invention in order to optimize the lithographic performance of photoresist compositions of the instant invention.
  • the ionic photoacid generators can be present in a catalytically effective amount to initiate polymerization (for negative photoresists) or depolymerization or deblocking (for positive photoresists), and is generally in the range of 0.01 to 20 wt. %, preferably 0.1 to 10 wt. %, most preferably 1 to 5 wt.% of the total polymeric resin composition; i.e., the total composition excluding any solvent that may be present.
  • the present invention also provides polymerizable coating compositions comprising (1) at least one of cationically polymerizable monomers, ethylenically-unsaturated free radically polymerizable monomers, or mixtures thereof and (2) an ionic PAG of the present invention.
  • the present invention also provides a method for the polymerization comprising the steps of:
  • the present invention further provides a method for preparing coated articles containing the cured composition of the invention comprising the steps of:
  • Solvent preferably organic solvent
  • Solvent may be present in an amount up to 99 weight percent, preferably in the range of 0 to 90 weight percent, and most preferably in the range of 0 to 75 weight percent, of the total composition.
  • the curable composition could contain additional adjuvants such as silica fillers, glass bubbles and tougheners. These adjuvants add toughness to and reduce the density of the cured composition. Generally shorter chain polyols would be used to give toughness through chain extension of the cured epoxy. Too long a chain diol generally would produce too soft a cured composition that would not have the strength needed for structural/semi-structural applications. Using polyols having high hydroxyl functionality (e.g., greater than three) could produce an over-crosslinked material resulting in a brittle adhesive.
  • additional adjuvants such as silica fillers, glass bubbles and tougheners.
  • magnetic particles must be added to the curable composition.
  • Magnetic media need to be coated onto a suitable substrate, generally a polymeric substrate like polyester.
  • the coatings are very thin so that sufficient carrier solvent must be added to allow the production of a suitably thin, even coating.
  • the coating must cure rapidly so a fast initiator system and curable materials must be chosen.
  • the cured composition must have a moderately high modulus so the curable materials must be selected appropriately.
  • Abrasion resistant coatings are generally hard and require a significant portion of the formulation to be a hard resin, which are generally short chain length and have high functionality. Coatings undergoing some flex require toughness that can be obtained by lowering the crosslink density of the cure formulation. Clear coatings require the cured resins to have little to no phase separation. This obtained by controlling the compatibility of the resins or controlling phase separation by cure rate. Adjuvants could be added to these coating formulations in an amount effective for their intended use.
  • the ionic photoacid generators can be present in a catalytically effective amount to initiate polymerization, and is generally in the range of 0.01 to 20 weight percent (wt %), preferably 0.1 to 10 wt % of the overall polymeric resin composition; i.e., the total composition excluding any solvent that may be present.
  • a wide variety of monomers can be energy polymerized using the photoacid generators of the invention. Included are monomers selected from the group consisting of cationically polymerizable monomers, free-radically-polymerizable monomers, and acid-catalyzed step-growth polymerizable monomers. Preferred monomers are acid-catalyzed step-growth polymerizable monomers and cationically polymerizable monomers, with the more preferred monomers being the cationically polymerizable monomers.
  • Suitable cationically polymerizable monomers and/or oligomers typically contain at least one cationically polymerizable group such as epoxides, cyclic ethers, vinyl ethers, vinylamines, side-chain unsaturated aromatic hydrocarbons, lactones and other cyclic esters, lactams, oxazolines, cyclic carbonates, cyclic acetals, aldehydes, cyclic amines, cyclic sulfides, cyclosiloxanes, cyclotriphosphazenes, certain olefins and cycloolefins, and mixtures thereof, preferably epoxides and vinyl ethers.
  • a cationically polymerizable group such as epoxides, cyclic ethers, vinyl ethers, vinylamines, side-chain unsaturated aromatic hydrocarbons, lactones and other cyclic esters, lactams, oxazolines,
  • epoxy resins are "electronic grade,” that is, low in ionic contaminants.
  • Useful epoxy resins can include propylene oxide, epichlorohydrin, styrene oxide and epoxies based upon bisphenol A, such as, EPON-828-LSTM electronic grade epoxy resins available from Shell Chemicals, or novolac epoxies, such as, EPON-164TM (also available from Shell Chemicals) or their equivalents from other manufacturers.
  • Additional useful epoxy resins include dicylopentadiene dioxide, epoxidized polybutadiene such as the Poly BDTM resins available from Elf Atochem, 1,4-butanediol diglycidyl ether, and resorcinol diglycidyl ether.
  • cycloaliphatic epoxies such as cyclohexene oxide and the ERLTM series of resins available from Union Carbide, such as vinylcyclohexene dioxide (ERL-4206TM), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (ERL-4221TM), bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate (ERL-4299TM); 1,4-butanediol diglycidyl ether, (for example, Heloxy 67TM available from Shell Chemical), polyglycidyl ether of phenol-formaldehyde novolak (e.g ., DBR-431TM and DER-438TM, available from Dow Chemical Co., polyglycol diepoxide ( e.g ., DER 736TM, available from Dow Chemical Co.), and mixtures thereof as well as mixtures thereof with co-curatives,
  • acid anhydrides such as maleic anhydride, cyclopentanetetracarboxylic acid dianhydride, pyromellitic anhydride, cis-1,2-cyclohexanecarboxylic acid anhydride, and mixtures thereof.
  • Epoxy resins preferred for use in conductive adhesives are the glycidyl ether type of resins, particularly in formulations where stabilizers are present.
  • hydroxy-functional materials can be added.
  • the hydroxyl-functional component can be present as a mixture or a blend of materials and can contain mono- and poly-hydroxyl containing materials.
  • the hydroxyl-functional material is at least a diol.
  • the hydroxyl-functional material can aid in chain extension and preventing excess crosslinking of the epoxy during curing, e.g ., increasing toughness of the cured composition.
  • useful hydroxyl-functional materials include aliphatic, cycloaliphatic or alkanol-substituted arene mono- or poly-alcohols having from about 2 to about 18 carbon atoms and two to five, preferably two to four hydroxy groups, or combinations thereof.
  • Useful mono-alcohols can include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 1-pentanol, neopenyl alcohol, 3-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-phenoxyethanol, cyclopentanol, cyclohexanol, cyclohexylmethanol, 3-cyclohexyl-1-propanol, 2-norbornanemethanol and tetrahydrofurfuryl alcohol.
  • Polyols useful in the present invention include aliphatic, cycloaliphatic, or alkanol-substituted arene polyols, or mixtures thereof having from about 2 to about 18 carbon atoms and two to five, preferably two to four hydroxyl groups.
  • polystyrenediol examples include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,6-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, diethlene glycol, triethylene glycol, tetraethylene glycol, glycerine, 2-ethy-2-(hydroxymethyl)
  • Higher molecular weight polyols include the polyethylene and polypropylene oxide polymers in the molecular weight (M n ) range of 200 to 20,000 such as the CarbowaxTM polyethyleneoxide materials available from Union Carbide, caprolactone polyols in the molecular weight range of 200 to 5,000 such as the ToneTM polyol materials available from Union Carbide, polytetramethylene ether glycol in the molecular weight range of 200 to 4,000, such as the TerathaneTM materials available from DuPont, polyethylene glycol, such as PEG 200 available from Union Carbide, hydroxyl-terminated polybutadiene resins such as the Poly BDTM materials available from Elf Atochem, phenoxy resins, such as those commercially available from Phenoxy Associates, Rock Hill, SC, or equivalent materials supplied by other manufacturers.
  • M n molecular weight
  • Cationically-polymerizable vinyl and vinyl ether monomers are also particularly useful in the practice of this invention and are described in U.S. Patent No. 4,264,703 .
  • Suitable free-radically polymerizable compounds containing at least one ethylenically unsaturated double bond may be monomers and/or oligomers, such as (meth)acrylates, (meth)acrylamides, and other vinyl compounds capable of undergoing free-radical polymerization. Such monomers and specific examples are more fully described in U.S. Patent No. 4,985,340 .
  • Such monomers include mono-, di-, or polyacrylates and methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, isooctyl acrylate, acrylic acid, n-hexyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, -tetraacrylate and -tetramethacrylate, the bis-acrylates and bis-methacrylates of poly
  • Acid-catalyzed step growth polymerizations include, but are not limited to, the reaction of multifunctional isocyanates (polyisocyanates) with multifunctional alcohols (polyols) to form polyurethanes, the reaction of multifunctional epoxies with multifunctional alcohols, and the cyclotrimerization of multifunctional cyanate esters to crosslinked polytriazine resins.
  • Suitable multifunctional cyanate esters that can be cured by catalyzed cyclotrimerization, using catalysts of this invention are described in U.S. Patent Nos. 5,143,785 and 5,215,860 .
  • Suitable multireactive monomers that can be cured by catalysts of the invention include glycidyl (meth)acrylate, hydroxy(alkyl) (meth)acrylates such as hydroxyethyl acrylate, isocyanatoethyl methacrylate, and the like.
  • the polymerizable components can be present in any proportion preferably with the minor component comprising at least 1.0 wt %.
  • compositions of this invention Mixtures of aforementioned classes of monomers with additives such as tackifiers, hardeners, co-curatives, curing agents, stabilizers, sensitizers etc. can also be used in the polymerizable compositions of this invention.
  • adjuvants such as pigments, abrasive granules, stabilizers, light stabilizers, antioxidants, flow agents, bodying agents, flatting agents, colorants, inert fillers, binders, blowing agents, fungicides, bacteriocides, surfactants, plasticizers, and other additives as known to those skilled in the art can be added to the compositions of this invention.
  • compositions containing radiation-sensitive catalysts or initiators can be added in an amount effective for their intended purpose, as long as they do not interfere with the polymerization of the compositions of the invention. Additionally, in compositions containing radiation-sensitive catalysts or initiators it is preferable that the adjuvants do not absorb radiation to which the catalysts or initiators are responsive.
  • Stabilizing additives useful in the compositions are described in detail in US Pat. No. 5,554,664 (Lamanna et al. ).
  • Solvents preferably organic, can be used to assist in dissolving the curing agent in the polymerizable monomers described supra and as a processing aid.
  • Representative solvents include acetone, methyl ethyl ketone, cyclopentanone, methyl cellosolve acetate, methylene chloride, nitromethane, methyl formate, acetonitrile, gamma-butyrolactone, 1,2-dimethoxyethane (glyme), 3-methyl sulfolane, and propylene carbonate.
  • an inert support such as silica, alumina, clays, etc., as described in U.S. Patent No. 4,677,137 .
  • energy-induced polymerization of the polymerizable compositions of this invention which incorporate a latent, light or radiation sensitive catalyst or initiator, (i.e. PAG) may be carried out at room temperature for the majority of energy curable compositions, although low temperature (e.g., -10°C) or elevated temperature (e.g., 30° to 400°C, preferably 50° to 300°C) can be used to subdue the exotherm of polymerization or to accelerate the polymerization, respectively.
  • Low temperature e.g., -10°C
  • elevated temperature e.g., 30° to 400°C, preferably 50° to 300°C
  • Temperature of polymerization and amount of catalyst will vary and be dependent on the particular curable composition used and the desired application of the polymerized or cured product.
  • curing agent ionic PAG
  • amount of curing agent (ionic PAG) to be used in this invention should be sufficient to effect polymerization of the monomers (i.e., a catalytically effective amount) under the desired use conditions.
  • amount generally will be in the range of about 0.01 to 20 wt %, and preferably 0.1 to 10 wt %, based on the weight of the curable composition.
  • curable composition means the composition including all monomers, activators/initiators, additives, adjuvants, sensitizers and other non-solvent components of the polymerization mixture.
  • any source of radiation including accelerated particles (e.g., electron beam or ion beam radiation), x-ray, extreme-UV, deep-UV, mid-UV near-UV and visible radiation can be used.
  • Suitable sources of radiation include fluorescent lamps, mercury vapor discharge lamps, carbon arcs, tungsten lamps, xenon lamps, various lasers and laser sources, e-beam sources, ion beam sources, sunlight, etc.
  • the required amount of exposure to activate the PAG and drive the chemical amplification process is dependent upon such factors as the identity and concentrations of the ionic PAG, the particular monomers or functional polymers present, the temperature and thickness of the exposed material, the type of substrate, the intensity of the radiation source and the amount of heat associated with the radiation.
  • photoacid generators of the present invention can provide exceptionally strong catalytic activity when activated as compared to other commonly known catalyst and photocatalyst systems. This is particularly true where monomers polymerizable by cationic addition polymerization or acid-catalyzed step-growth polymerization are used and in high activation energy photoresists which require strong acid photocatalysts.
  • TGA Thermal gravimetric Analysis
  • TGA was performed on a Perkin-Elmer Instruments TGA Model 7 in an open platinum pan.
  • the onset of thermal decomposition, T d was taken as the thermal decomposition temperature of the photoacid generators and was determined under nitrogen atmosphere using a temperature ramp of 10°C per minute. The onset temperature was determined by the intersection of tangents to the low temperature portion of the baseline and the first inflection point in the wt% vs. temperature curve.
  • Photo-DSC/DSC Standard (hermetic) liquid sample pans were used. Sample size was kept in the 6 to 8 mg range. Samples were tested using a Dupont Photo-DSC/DSC instrument (available from DuPont, Wilmington, DE). The light source was a 200W Hg lamp that delivered about 60mw/cm 2 at the sample. Samples were exposed in open pans for 5 minutes to the light source at 30°C then removed from the instrument, sealed and a standard DSC scan run at 10°C/minute to 300°C. A separate DSC experiment was carried out using a sealed sample pan and no prior light exposure to determine the dark reactivity of these PAGs. Comparison of the DSC traces before and after light exposure enables differentiation between the thermal reactivity of the PAGs (in the dark) and their photochemical activity.
  • 1,3-hexafluoropropylenedisulfonic anhydride (7.1 g, 0.024mole) and methylene chloride (5 mL) were charged to a dry Schlenck tube equipped with a magnetic stir bar and a rubber septum.
  • the resulting solution was cooled to 0°C in an ice bath followed by dropwise addition of anhydrous diallylamine (5.78 g, 0.059 mole) with stirring. After 30 minutes, the reaction solution was allowed to warm to room temperature. A lower liquid phase was separated and discarded.
  • the remaining methylene chloride solution was evaporated to dryness at 64°C under vacuum to remove all volatiles.
  • the light brown crystalline residue that remained was dissolved in a solution of 3.0g lithium hydroxide hydrate in deionized water (300 mL). This solution was distilled through a Vigreux column equipped with a Dean Stark trap. A low boiling, low-density phase distilled first (diallylamine), followed by water. A total of 100 mL of distillated was collected and reserved.
  • the aqueous product solution remaining in the still pot was allowed to cool to room temperature and then treated with dry ice to convert all residual LiOH to Li 2 CO 3 , resulting in a final pH of 7.0.
  • the aqueous mixture was treated with CeliteTM (available from Sigma-Aldrich) and filtered by suction through a glass frit to yield a light yellow filtrate.
  • the aqueous filtrate was evaporated to dryness using a rotary evaporator, yielding a white solid residue.
  • the solid was dissolved in 200mL of acetonitrile and filtered by suction through a 0.2 micron TefsepTM membrane.
  • the filtrate was again evaporated to dryness at 70°C, 20 Torr (2.7 kPa) to yield 5.76g of white solid, corresponding to 60% yield of the desired product.
  • the organic phase was dried by stirring over high purity silica gel (5 g) for an hour.
  • the dried solution was filtered by suction through a 0.2 micron Tefsep TM filter to remove silica gel.
  • the pad of silica gel was washed with two additional 70mL portions of the methylene chloride/methyl-t-butyl ether mixture and the combined filtrate was evaporated to dryness on a rotary evaporator at 50°C and approximately 20 Torr (2.7 kPa).
  • the anion contained greater than 99% linear (-CF 2 -) 3 groups.

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US20050158655A1 (en) 2005-07-21
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EP1556740A2 (en) 2005-07-27
WO2004042473A2 (en) 2004-05-21
AU2003286528A1 (en) 2004-06-07
JP2006504785A (ja) 2006-02-09
ATE550692T1 (de) 2012-04-15
US6841333B2 (en) 2005-01-11
US20040087690A1 (en) 2004-05-06
WO2004042473A3 (en) 2004-07-01
KR20050071645A (ko) 2005-07-07
US7078444B2 (en) 2006-07-18

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